Organic electroluminescent device based on 2,5-diaminoterephthalic acid derivatives

ABSTRACT

The application relates to an organic electroluminescent device which contains 2,5 diaminoterephthalic acid derivatives of formula 1a as emitter substances in one or several emitter layers in a pure or doped manner. The ring A is a triple unsaturated benzole ring wherein R 4′  and R 8′  are equal to zero or ring A is a double unsaturated ring respectively provided with a double bond in the 1,2 position and 4,5-position, and wherein R 10  is a nitrile radical —CN or a radical C(═X 1 )—X 2 R 1 ; R 11  is a nitrile radical —CN or a radical —C(═X 3 )—X 4 R 5 , X 1  and X 3  are oxygen, sulphur or imino, X 2  and X 4  are oxygen, sulphur or optionally substituted amino, R 1  to R 8 , R 4′  and R 8′  are H, C1-C20-alkyl, aryl, heteroaryl, R 4  and R 8  can also be halogen, nitro, cyanogen or amino, R 2  to R 4 , R 6 —R 8 , R 4′  and R 8′  can also be trifluoromethyl or pentafluorophenyl, and wherein certain radicals can form a saturated or unsaturated ring. The novel devices are characterised by narrow emission bands, low driver voltages, high photometric efficiency and high thermal stability within a broad spectral range.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority of German patent application no. DE10141266.5, filed Aug. 21, 2001, and international patent applicationno. PCT/DE02/03110 (entitled Organic Electroluminescent Device Based on2,5-Diaminoterephthalic Acid Derivatives), filed August, 2002, theentire disclosures of which are incorporated herein by reference and forall purposes.

The present application relates to a new organic electroluminescentdevice based on 2,5-diaminoterephthalic acid derivatives. Saidderivatives are emitter substances for organic light-emitting diodes(OLED). Organic light-emitting diodes, which have long been known, usethe electroluminescence of certain organic compounds. An OLED'sstructure and the tasks of its individual layers are exemplified inFIG. 1. A layer sequence of organic substances is arranged between twoelectrodes, of which at least one must be translucent, each organicsubstance having a specific function within the device.

-   -   The cathode consists of a base metal or an alloy (e.g. aluminium        or calcium) and has the function of injecting electrons;    -   The buffer layer consists of certain metal salts or the oxides        thereof, e.g. LiF, and has the function of improving the        electron injection into the layer 3;    -   The electron conductor can e.g. consist of Alq3        (tris-(8-hydroxychinolinato)-aluminium) and conducts the        electrons from the cathode to the emitting layer or the hole        conductor inside the device;    -   The hole conductor mainly consists of triphenylamine        derivatives; several hole conductor layers can be provided whose        characteristics are adapted to the device and whose function is        to transport the holes to the emitting layer;    -   The anode consists of ITO which injects the holes into the hole        transport layer;    -   The substrate consists of a transparent material, e.g. glass.

An arrangement of the type described above emits green light generateddue to the excitation of Alq3 by the excitons formed from the holes andelectrons.

However, such a simple arrangement has several drawbacks:

-   -   1. Alq3 only emits light in the green spectral range;    -   2. The emission band of Alq3 is too broad.

Said drawbacks can in part be eliminated by doping. This means that oneor more substances are co-evaporated during the diode's productionprocess. In general, these substances are contained in the Alq3 layer inan amount ranging up to a few percent. Said co-evaporation process isdifficult to control.

This application relates to new emitter substances which eliminate theknown drawbacks of Alq3 both as an emitter substance and a host materialfor dopants. As a consequence, Alq3 is generally required as an electronconductor only. The new emitter substances are characterized by:

-   -   1. narrower emission bands;    -   2. the devices cover a broad spectral range due to the fact that        different substances are used, either in layers separated from        one another or in mixed layers;    -   3. low driver voltages;    -   4. high photometric efficiency (low power consumption);    -   5. high luminance (emission intensity);    -   6. high thermal stability.

For the purposes of this application, the term “device” relates to anarrangement in which the substrate and layers are arranged on top of oneanother according to FIG. 1 or 2, but which has not yet beenincorporated into a light-emitting diode. Such a device can in principlehave the structure shown in FIG. 1 or 2. In said devices, the2,5-diaminoterephthalic acid derivatives can be co-evaporated eitheralone or conjointly with other compounds, optionally even with knowncompounds, to obtain emitters. These emitters are used in combinationwith known hole conductors.

The present application provides new organic electroluminescent devicesusing improved emitter substances. According to one embodiment, theorganic electroluminescent device contains 2,5-diaminoterephthalic acidderivatives of the following formula 1a in one or several emitter layersin a pure or doped form in a device

wherein the ring A is a triply unsaturated benzene ring wherein R^(4′)and R^(8′) are omitted, or the ring A is a doubly unsaturated ringhaving a double bond in the 1,2-position and in the 4,5-position, and

-   wherein R¹⁰ represents a nitrile radical —CN or a radical    —C(═X¹)—X²R¹,-   R¹¹ is a nitrile radical —CN or a radical —C(═X³)—X⁴R⁵,-   wherein-   X¹ and X³ can be the same or different atoms or groups, such as    oxygen, sulphur, imino, preferably oxygen;-   X² and X⁴ can be the same or different atoms or groups, such as    oxygen, sulphur, amino, wherein the amino nitrogen can be    substituted with alkyl having 1 to 20 C-atoms, preferably C1 to C8,    or with aryl, e.g. phenyl, naphthyl, or with heteroaryl, e.g.    cumaryl, pyridyl, chinolyl, indolyl, carbazolyl, imidazolyl,    thienyl, thiazolyl, furyl, oxazolyl;-   R¹ to R⁸, R^(4′) and R^(8′) can be the same or different    substituents, such as hydrogen, alkyl having 1, to 20 atoms,    preferably C1 to C8; aryl, e.g. phenyl, naphthyl, as well as    heteroaryl, e.g. cumaryl, pyridyl, chinolyl, indolyl, carbazolyl,    imidazolyl, thienyl, thiazolyl, furyl, oxazolyl, and the aforesaid    radicals can be substituted singly or doubly with atoms or groups,    e.g. di-C1-C3-amino or alkoxy with alkyl radicals C1 to C10,    preferably C1-C4; C1-C4 alkyl, cyano, fluorine, chlorine, bromine or    iodine as well as phenyl;-   R⁴ and R⁸ can also be the same or different substituents, such as    halogen, nitro, cyano or amino; R² to R⁴, R⁶ to R⁸, R^(4′) and    R^(8′) can also be trifluoromethyl or pentafluorophenyl, and wherein    the following radicals can form a saturated or unsaturated ring-   X¹ and X², R¹ and R², R² and X², R² and R³, R³ and R⁴, R⁴ and X³, X³    and X⁴, R⁵ and X⁴, R⁶ and X⁴, R⁶ and R⁷, R⁷ and R⁸, R⁸ and X¹, R³    and R^(4′), R⁷ and R^(8′), R⁴ and R^(4′), and R⁸ and R^(8′), to    which rings further rings can be fused.

It is preferred that R², R³, R⁶ and R⁷ be trifluoromethyl orpentafluorophenyl, R⁴ and R⁸ be halogen, nitro, cyano or amino, and theother substituents have the meaning indicated above. It is particularlypreferred that R⁴ and R⁸ be trifluoromethyl or pentafluorophenyl, andthe other substituents have the meaning indicated above.

As regards spelling in the following text, R¹⁻⁸ means R¹ to R⁸; X^(2,4)means X² and X⁴; R^(4′,8′) means R^(4′) and R^(8′).

The application also relates to new 2,5-diaminoterephthalic acidderivatives of the formula 19

wherein X¹ is O and X² is O or N; R² and R⁶ are methylene (—CH₂—) whichcan be substituted with trifluoromethyl, R³ and R⁷ are the same ordifferent, H, C1-C8 alkyl, aryl or heteroaryl, and R⁴ and R⁸ are thesame or different, H, alkyl, aryl or trifluoromethyl.

It is particularly preferred that alkyl be C1-C4 alkyl, aryl be phenylor naphthyl, and heteroaryl be pyridyl, thienyl or furyl.

In general, it is preferred that substituents arranged opposite oneanother, such as X¹ and X³, X² and X⁴, R¹ and R⁵, R² and R⁶, R³ and R⁷,R⁴ and R⁸, R^(4′) and R^(8′), and R¹⁰ and R¹¹, are the same, i.e. notdifferent, in the structures described herein. The electroluminescentdevices according to one embodiment preferably contain 2 to 3 differentsubstances which are mixed with one another in one device.

Now, preferred structures will be listed, wherein in the structures 1

The emitter substances of formula 1, i.e. derivatives of2,5-diaminoterephthalic acid, can be obtained by reacting esters ofcyclohexane-2,5-dione-1,4-dicarboxylic acid with primary anilines oramines, subsequent oxidation and, optionally, further modification. Saidderivatives can be processed into cyclized derivatives in a manner knownper se, as shown e.g. in Formula Diagrams I and II.

The compounds of formula 3 can be produced by reacting the respective2,5-diaminoterephthalic acid amides with dehydrating agents.

In order to produce the compounds of formula 4, wherein R⁴ and R⁸ aswell as R^(4′) and R^(8′) are not H, the esters of2,5-diaminocyclohexane-1,4-dicarboxylic acid are converted intohydrazides and reacted with potassium hexacyanoferrate(III) in order toobtain aldehydes. These 2,5-diaminocyclohexane-1,4-dicarbaldehydes canbe converted into oximes which are reacted with formic acid in order toobtain the compounds of formula 4.

Examples of the new emitters according to formula 1 are listed in Table1 below.

The new emitters are used in a device comprising or not comprising anelectron transport layer, wherein the layers in a device can be arrangedas shown in FIG. 2:

-   -   1. The substrate consists of a transparent material, e.g. glass;    -   2. The anode consists of ITO which injects the holes into the        hole transport layer;    -   3./4. The hole conductor mainly consists of triphenylamine        derivatives; several hole conductor layers can be provided whose        characteristics are adapted to the device;    -   5. Between the hole conductor and the electron conductor, one or        more emitter layers are arranged;    -   6. The electron conductor can e.g. consist of Alq3 and conducts        the electrons from the cathode to the emitting layer or the hole        conductor inside the device;    -   7. The buffer layer consists of certain metal salts or the        oxides thereof, e.g. LiF, and improves the electron injection        into the layer 6;    -   8. The cathode consists of a base metal or an alloy (e.g.        aluminium or calcium).

Typically, the emitter layers are 3-10 nm thick, preferably 4-6 nm. Theemission wavelengths depend on the chemical structure in acharacteristic manner, i.e. electronic and steric factors of themolecules obviously influence the wavelength of the emitted light andthe performance achieved. The wavelengths of the examples listed inTable 2 range between 538 nm and 618 nm.

In order to achieve mixed colours, the new emitters of formulas 1.0-58.0can be arranged on top of one another, either in the form of severallayers each of which consists of an emitter material in its pure form(FIG. 2) or in the form of one or several layer(s) in which the emittermaterials are provided in a mixed form.

The layers comprising the new emitters of formulas 1.0-58.0 can be dopedwith known emitter materials, as shown in FIG. 1.

The new emitters of formulas 1.0-58.0 can be used in devices comprisinghole conductors known per se (59 and 60) and other components. Typicalexamples are shown in FIGS. 1 and 2.

4,4′,4″-tris(N-(α-naphthyl)-N-phenylamino)-triphenylamine (1-NAPHDATA)

N,N′-di(α-naphthyl)-N,N′-diphenylbenzidine (α-NPD)

The devices based on the new emitters can be produced in a manner knownper se, i.e. by vacuum deposition at between 1 and 10⁻⁹ torrs.

Alternatively, the devices can be produced by solution coating, e.g. webcoating or spin coating. Here, the new emitters of formulas 1.0-58.0 canbe applied either as the pure substance or as a dopant contained in asuitable polymer.

Surprisingly, it has been found that particularly efficient devices canbe produced using substances of the formula 1.0 which have beensubstituted with fluorine. A remarkably high photometric efficiency isobserved in these cases. Using the substance 1.2, a device emitting aspectrally nearly pure green is obtained.

Experimental Part

The following examples are intended to illustrate the present inventionin more detail, but do by no means limit the same.

EXAMPLE 1 (Substances 2.1, 2.3-2.5)

-   -   0.06 mol cyclohexane-2,5-dione-1,4-dicarboxylic acid diester is        suspended in a mixture of 200 ml glacial acetic acid and 200 ml        alcohol (corresponding to the ester component). In a nitrogen        atmosphere, 0.135 mol of a primary amine or aniline is speedily        added. The reaction mixture is refluxed for 5-8 hours while        stirring thoroughly. Anilines which have been substituted with        an acceptor require longer reaction times.

In the case of anilines, the crude product can be isolated by suckingoff the cooled-down reaction mixture, thoroughly washing it withmethanol and drying. Aliphatic amines form highly soluble products, i.e.the solvent must be separated almost completely using a rotaryevaporator. The crude product is added into methanol, thoroughly cooled,sucked off and dried.

EXAMPLE 2 (Substances 1.1, 1.3-1.5)

The esters of dihydroterephthalic acid obtained in Example 1 areoxidized.

Yields of up to 95% are achieved during isolation. In order to purifythe separated crude product, it can be recrystallized from DMF, toluene,chloroform or methanol. The substances obtained are sublimable.

EXAMPLE 3 (Substances 19.1-19.4)

The esters obtained according to Example 2 are saponified in mixtures ofn-propanol and water. 0.01 mol terephthalic acid diester is suspended inapprox. 50 ml n-propanol, and 50 ml water containing 0.03 mol potassiumhydroxide is added. The suspension is refluxed until a clear solution isobtained. Once another 2 hours have passed, the liquid is sucked off. Inorder to neutralize the solution, approx. 5 ml glacial acetic acid isadded dropwise. The acid obtained is washed with methanol and dried.

In order to produce the substances 19.1-19.4, 0.01 mol of theterephthalic acid obtained is refluxed for 2 hours in 100 ml glacialacetic acid to which 15 ml formaldehyde solution (37%) has been added.The reaction products are separated and washed with methanol. They arerecrystallized from acetonitrile or chloroform. The substances obtainedcan be purified by sublimation.

EXAMPLE 4 (Substance 1.2)

In order to obtain compounds of this type, the respective terephthalicacid ester (Example 2) can be alkylated. 0.05 mol terephthalic acidester is suspended in 350 ml anhydrous DMSO, and 18.63 g (0.131 mol)methyl iodide is added. 6.1 g (0.152 mol) 60% sodium hydride in paraffinis added in portions at a temperature ranging between 20 and 23° C. andwhile stirring thoroughly. Once a reaction time of approx. 5 hours haspassed, the colour of the solid constituents has changed from orange topure yellow. Now, approx. 200 ml methanol is added to the mixture,thereby considerably improving filterability.

The separated yellow reaction product is thoroughly washed with methanoland dried. A pure product is obtained by recrystallization from toluene.

EXAMPLE 5 (Device: Substance 19.4)

A 55 nm thick layer of 4,4′,4″-tris(N-(α-naphthyl)-N-phenylamino)-triphenylamine and another 5 nmthick layer of N,N′-di(α-naphthyl)-N,N′-diphenylbenzidine were depositedonto a structured ITO glass substrate measuring 50×50 mm². Onto thesehole transport layers, 5 nm 1,6-bis(2,4-dimethoxyphenyl)-benzo[1,2-d;4,5-d′]-1,2,6,7-tetrahydro-bis[1,3]oxazine-4,9-dione (19.4) isdeposited.

In addition, a 30 nm thick layer oftris-(8-hydroxychinolinato)-aluminium is now applied onto this emitterlayer, followed by a very thin buffer layer (0.5 nm) of lithium fluorideand finally aluminium. The arrangement was tested applying an adjustablevoltage between 0 and 15 V. The device emits a wavelength of 578 nm(yellow). A luminance (emission intensity) of 100 cd/m² was achieved at5.0 V. The maximum luminance (emission intensity) achieved was 11,400cd/m².

EXAMPLE 6 (Device: Substance 1.21)

A device was produced according to Example 5, into which a 5 nm thicklayer of 2,5-bis-(N-(2,4-dimethoxyphenyl)amino)terephthalic acid diethylester was incorporated as emitter substance between the hole conductorand the electron conductor. The device was also tested applying anadjustable voltage between 0 and 15 V. The device emits a wavelength of618 nm (red). A luminance (emission intensity) of 100 cd/m² was achievedat 9.5 V. The maximum luminance (emission intensity) achieved was 644cd/m².

EXAMPLE 7 (Device: Substance 1.5)

The device has the same structure as those of Examples 5 and 6. Theemitter substance used was 2,5-bis-(N-phenylamino)-terephthalic aciddiethyl ester. Once again, the device was tested applying an adjustablevoltage between 0 and 15 V. The device emits a yellow light (578 nm). Aluminance (emission intensity) of 100 cd/m² was achieved at 5.6 V. Themaximum luminance (emission intensity) recorded was 5,300 cd/m².

EXAMPLE 8 (Device: Substance 1.2)

Analogously to Examples 5-7 and according to the same structuralprinciple, a 5 run thick layer ofN,N′-dimethyl-2,5-bis-(N-(2-fluorophenyl)-amino)terephthalic aciddimethyl ester was deposited onto the hole transport layers. Thearrangement (FIG. 2) was tested applying an adjustable voltage between 0and 15 V. The device emits a green light (λ_(max)=547 nm). A luminance(emission intensity) of 100 cd/m² was achieved at 5.4 V. The maximumluminance (emission intensity) achieved was 17,700 cd/m².

-   -   1. The substrate consists of glass;    -   2. The anode consists of ITO;    -   3. 1-Naphdata is applied as hole conductor;    -   4. Another hole conductor layer consists of α-NPD;    -   5. One or several emitter layers are arranged between the hole        conductor and the electron conductor;    -   6. The electron conductor can e.g. consist of Alq3;    -   7. The buffer layer consists of LiF;    -   8. The cathode consists of a base metal or an alloy (e.g.        aluminium or calcium).

Typically, the emitter layers are 3-10 nm thick, preferably 4-6 nm.TABLE 2 Photometric parameters of selected emitter substances ¹⁾V ²⁾nmColour ³⁾cd/m² ⁴⁾cd/A ⁵⁾lm/W 1.21 9.2 629 red-white 1980 0.12 0.071.16*⁾ 9.3 634 red-white 3990 0.14 0.10 1.16 14.0 618 red 144 0.09 0.071.30 5.6 612 orange-red 12100 2.17 2.27 19.4 5.0 578 yellow 11400 2.041.72 1.5 5.6 578 yellow 5300 1.59 1.42 1.4 8.0 577 yellow 1410 0.81 0.3719.3 6.5 565 yellow-green 4530 0.72 0.49 1.3 8.1 577 yellow-green 43302.77 1.52 19.7 10.2 yellow-green 474 0.26 0.10 1.34 3.5 550 green 365001.00 9.21 1.36 5.7 546 green 18100 6.60 4.34 1.2 5.4 547 green 177007.70 4.93 1.38 6.4 546 green 11300 4.62 2.47 19.2 6.6 564 green 60100.89 0.66 19.1 6.7 540 green 4680 3.05 1.70 19.6 8.6 545 green 2610 0.520.36 1.29 11.1 564 green 1330 1.59 0.47 1.1 7.1 538 green 1300 0.48 0.221.33 10.3 563 green 1100 1.53 0.54 1.31 10.8 566 green 754 1.60 0.5319.8 13.4 green 273 1.20 0.70 19.11 14.4 532 green 144 0.03 0.0119.5 >20.0 540 green 8 0.30 0.28 19.9 >15.0 544 green 64 0.58 0.13¹⁾voltage at 100 cd/m²²⁾λ_(max) of electroluminescence³⁾max. luminance (emission intensity)⁴⁾max. photometric efficiency⁵⁾max. performance efficiency

TABLE 3 Absorption and emission maxima of selected emitter substancesλ_(max) λ_(em) λ_(max) λ_(em) λ_(max) λ_(em) (solid) (solid) (solid)(solid) (solid) (solid) 1.6 614 1.19 435 531 1.6 623 1.7 597 1.4 59919.6 592 1.8 604 1.20 596 1.28 588 1.10 626 19.1 475 564 1.3 595 1.11596 19.4 460 598 1.24 612 1.12 586 1.5 465 582 19.8 453 583 1.1 547 1.21495 625 1.2 558 1.13 559 19.5 612 .5 496 622 1.14 543 1.23 573 1.15 6051.24 564 1.16 500 635 1.25 605 1.17 596 1.26 602 1.18 617 19.3 582λ_(max): absorption maximumλ_(em): emission maximumλ_(ell): maximum of electroluminescence

TABLE 4 Absorbance coefficients ε of selected emitter substances #λ_(max) (nm) ε (l · mol⁻¹ cm⁻¹) Solvent 1.16 489 6000 CHCl₃ 1.5 469 6640CHCl₃ 1.34 403 4744 NMP 19.6 452 5250 CHCl₃ 19.5 474 4670 CHCl₃ 19.7 4335450 NMP 1.17 472 6410 CHCl₃ 1.15 486 5930 CHCl₃ 1.12 460 5930 CHCl₃1.11 481 6840 CHCl₃ 1.8 472 6450 CHCl₃ 1.7 474 6550 CHCl₃ 19.1 434 4700NMP 1.30 493 5450 NMP 1.27 482 6800 CHCl₃

TABLE 5 Absorption maxima of selected emitter substances in solutionλ_(max) (NMP) λ_(max) (NMP) λ_(max) (NMP) 1.6 482 1.19 417 1.6 481 1.7476 1.4 468 19.6 452 1.8 463 1.20 461 1.28 473 1.9 652 19.1 435 1.3 4511.10 509 19.4 458 1.24 480 1.11 475 1.5 451 1.30 493 1.12 445 1.21 4791.34 403 1.1 413 1.22 505 .5 461 1.13 427 19.5 472 1.43 496 1.14 4281.23 432 1.15 482 1.24 446 1.16 494 1.25 487 1.17 464 1.26 482 1.18 46419.3 447

TABLE 6 DSC values of selected emitter substances # DSC peak in ° C.19.3 260.0 1.6 269.1 1.7 171.3 1.8 227.8 1.11 192.1 1.12 172.2 1.15232.0 1.17 166.5 19.1 325.7 1.16 183.3 1.34 254.7 19.1 325.7 1.27 182.5

Preparation and Measuring Conditions

a) Substrate: 125 nm ITO, approx. 13 Ω/sq and 85% tranmission, 50×50 mm²glass substrate (1.1 mm thick polished soda-lime float glass with SiO₂layer and 8 individual ITO anodes (active surface area: 2×2 mm²))

-   Purified 2×20 min in an ultrasonic bath with Aceton selectopur and    Methanol selectopur,-   3×snow jet cleaning (CO₂ ice crystals)-   O₂ plasma treatment (5 min at 450 W and 0.12 mbar)

b) Pressure (2-4)×10⁻⁵ mbar during deposition

-   Aluminium oxide ceramic crucible-   Deposition rate: 0.06 nm/s-   Layer thickness checked using a piezoelectric microbalance measuring    device-   Change of mask and intermediate aeration of the deposition chamber,    first with nitrogen and then with air-   Cathodes, 0.5 nm lithium fluoride (insulating) and 100 nm aluminium    each

c) The device according to FIG. 2 was introduced in a glove box, theactive OLED surface was positioned above calibrated V_(λ) siliconphotodiodes in a darkened measuring device, and the anode (ITO—) andcathode (Al—) contacts were brought in contact with gilded springelectrodes.

-   Programmable voltage supply (SMU) and digital multimeter for    recording and processing the OLED curve in a PC via GPIB-BUS and    LabView program-   Voltage pulse operation (pulses lasting is) between −10 V and +15 V    (0.5 V increments): current density-voltage curve and luminance    (emission intensity)-voltage curve as well as the calculated    photometric efficiency values (in cd/A) and performance efficiency    values (in lm/W) as a function of U

d) Wavelength of maximum by recording the electroluminescence spectrumusing an Xdap diode array spectrometer TABLE 1 2,5-diaminoterephthalicacid derivatives Substance X¹ X² R³ R¹

1.0

O O

—CH₃ 1.1

O O

—CH₃ 1.2

O O

—CH₃ 1.3

O O

—CH₃ 1.4

O O

—C₂H₅ 1.5

O O

—CH₃ 1.6

O O

—CH₃ 1.7

O O

—CH₃ 1.8

O O

—CH₃ 1.9

O O

—CH₃  1.10

O O

—CH₃  1.11

O O

—CH₃  1.12

O O

—CH₃  1.13

O O

—CH₃  1.14

O O

—CH₃  1.15

O O

—CH₃  1.16

O O

—CH₃  1.17

O O

—CH₃  1.18

O O

—CH₃  1.19

O O

—CH₃  1.20

O O

—CH₃  1.21

O O

—CH₃  1.22

O O

—CH₃  1.23

O O

—CH₃  1.24

O O —C₄H₉ —CH₃  1.25

O O

—CH₃  1.26

O O

—CH₃  1.27

O O

—CH₃  1.28

O O

—CH₃  1.29

O O

—CH₃  1.30

O O

—CH₃  1.31

O O

—CH₃  1.32

O O

—CH₃  1.33

O O

—CH₃  1.34

O O

—CH₃  1.35

O O

—CH₃  1.36

O O

—CH₃  1.37

O O

—CH₃  1.38

O O

—CH₃  1.39

O O

—CH₃  1.40

O O

—CH₃  1.41

O O

—CH₃  1.42

O O

—CH₃  1.43  1.44 O O

—CH₃  1.45 O O

—CH₃  1.46 O O

—CH₃  1.47 O O

—CH₃  1.48 O O

—CH₃  1.49 O O

—CH₃  1.50 O O

—CH₃  1.51 O O

—CH₃  1.52 O O

—CH₃  1.53 O O

—CH₃  1.54 O O

—CH₃  1.55 O O

—CH₃  1.56 O O

—CH₃  1.57 O O

—CH₃  1.58 O O

—CH₃  1.59 O O

—CH₃  1.60 O O

—CH₃  1.61 O O

—CH₃  1.62 O O

—CH₃  1.63 O O

—CH₃  1.64 O O

—CH₃  1.65 O O

—CH₃  1.67 O O

—CH₃  1.68 O O

—CH₃ Substance R² R⁴ X⁴ X³ R⁸

1.0

H H O O H 1.1

—CH₃ H O O H 1.2

H H O O H 1.3

H H O O H 1.4

H H O O H 1.5

H H O O H 1.6

H H O O H 1.7

H H O O H 1.8

H H O O H 1.9

H H O O H  1.10

H H O O H  1.11

H H O O H  1.12

H H O O H  1.13

H H O O H  1.14

H H O O H  1.15

H H O O H  1.16

H H O O H  1.17

H H O O H  1.18

—CH₃ H O O H  1.19

H H O O H  1.20

H H O O H  1.21

H H O O H  1.22

H H O O H  1.23

H H O O H  1.24

H H O O H  1.25

H H O O H  1.26

H H O O H  1.27

H H O O H  1.28

—CH₃ H O O H  1.29

H H O O H  1.30

—CH₃ H O O H  1.31

—CH₃ H O O H  1.32

—CH₃ H O O H  1.33

H O O H  1.34

H H O O H  1.35

—CH₃ H O O H  1.36

H H O O H  1.37

H O O H  1.38

H O O H  1.39

H O O H  1.40

H O O H  1.41

H O O H  1.42

H H O O H  1.43  1.44 —CH₃ H O O H  1.45 —CH₃ H O O H  1.46 —CH₃ H O O H 1.47 —CH₃ H O O H  1.48 —CH₃ H O O H  1.49 —CH₃ H O O H  1.50 —CF₃ H OO H  1.51 —CF₃ H O O H  1.52 —CF₃ H O O H  1.53 —CF₃ H O O H  1.54 —CF₃H O O H  1.55 —CF₃ H O O H  1.56

H O O H  1.57

H O O H  1.58

H O O H  1.59

H O O H  1.60

H O O H  1.61

H O O H  1.62

H O O H  1.63

H O O H  1.64

H O O H  1.65 —CH₃ H O O H  1.67

H O O H  1.68

H O O H Substance R⁵ R⁶ R⁷

1.0

—CH₃ H

1.1

—CH₃ —CH₃

1.2

—CH₃ H

1.3

—CH₃ H

1.4

—C₂H₅ H

1.5

—CH₃ H

1.6

—CH₃ H

1.7

—CH₃ H

1.8

—CH₃ H

1.9

—CH₃ H

 1.10

—CH₃ H

 1.11

—CH₃ H

 1.12

—CH₃ H

 1.13

—CH₃ H

 1.14

—CH₃ H

 1.15

—CH₃ H

 1.16

—CH₃ H

 1.17

—CH₃ H

 1.18

—CH₃ —CH₃

 1.19

—CH₃ H

 1.20

—CH₃ H

 1.21

—CH₃ H

 1.22

—CH₃ H

 1.23

—CH₃ H

 1.24

—CH₃ H —C₄H₉  1.25

—CH₃ H

 1.26

—CH₃ H

 1.27

—CH₃ H

 1.28

—CH₃ —CH₃

 1.29

—CH₃ H

 1.30

—CH₃ —CH₃

 1.31

—CH₃ —CH₃

 1.32

—CH₃ —CH₃

 1.33

—CH₃

 1.34

—CH₃ H

 1.35

—CH₃ —CH₃

 1.36

—CH₃ H

 1.37

—CH₃

 1.38

—CH₃

 1.39

—CH₃

 1.40

—CH₃

 1.41

—CH₃

 1.42

—CH₃ H

 1.43  1.44 —CH₃ —CH₃

 1.45 —CH₃ —CH₃

 1.46 —CH₃ —CH₃

 1.47 —CH₃ —CH₃

 1.48 —CH₃ —CH₃

 1.49 —CH₃ —CH₃

 1.50 —CH₃ —CF₃

 1.51 —CH₃ —CF₃

 1.52 —CH₃ —CF₃

 1.53 —CH₃ —CF₃

 1.54 —CH₃ —CF₃

 1.55 —CH₃ —CF₃

 1.56 —CH₃

 1.57 —CH₃

 1.58 —CH₃

 1.59 —CH₃

 1.60 —CH₃

 1.61 —CH₃

 1.62 —CH₃

 1.63 —CH₃

 1.64 —CH₃

 1.65 —CH₃ —CH₃

 1.67 —CH₃

 1.68 —CH₃

Substance X¹ X² R³ R¹  1.69 O O

—CH₃  1.70

—CH₃  1.71 O N

 1.72 O N

 1.73 O O

—CH₃  1.74 O O

—CH₃  1.75 O O

—CH₃

 17.0 

—CH₃

—CH₃ 17.3 

— 17.4 

—

5.0 5.1

11.0  11.1  O O

—CH₃ Substance R² R⁴ X⁴ X³ R⁸  1.69

H O O H  1.70

H O O H  1.71 H H N O H  1.72

H N O H  1.73 —CH₃

O O

 1.74

O O

 1.75

O O

 17.0  —CH₃ H

H —CH₃ H

H 17.3  —CH₃ H

H 17.4  —CH₃ H

H

5.0 5.1 —CH₃ H O O H

11.0  11.1  —CH₃ H

Substance R⁵ R⁶ R⁷  1.69 —CH₃

 1.70 —CH₃

 1.71

H

 1.72

 1.73 —CH₃ —CH₃

 1.74 —CH₃

 1.75 —CH₃

 17.0  —CH₃ —CH₃

—CH₃ —CH₃

17.3  — —CH₃

17.4  —CH₃

5.0 5.1 —CH₃ —CH₃

11.0  11.1  —CH₃ —CH₃

Substance X¹ X² R³ R² R¹

19.0 

O O

—CH₂— — 19.1 

O O

—CH₂— — 19.2 

O O

—CH₂— — 19.3 

O O

—CH₂— — 19.4 

O O

—CH₂— — 19.5 

O O

—CH₂— — 19.6 

O O

—CH₂— — 19.7 

O O

—CH₂— — 19.8 

O O

—CH₂— — 19.9 

O O

—CH₂— — 19.10

O O

—CH₂— — 19.11

O O

—CH₂— — 19.12 19.13 O O

—CH₂— — 19.14 O O

—CH₂— — 19.15 O O

—CH₂— — 19.16 O O

— 19.17 O O

—

7.0 7.1 O O

—CH₂— 7.2 O O

—CH₂—

13.0  13.1  O O

—CH₃ 13.2  O O

—CH₃ Substance R⁴ X⁴ X³ R⁸ R⁶ R⁵ R⁷

19.0 

H O O H —CH₂— —

19.1 

H O O H —CH₂— —

19.2 

H O O H —CH₂— —

19.3 

H O O H —CH₂— —

19.4 

H O O H —CH₂— —

19.5 

H O O H —CH₂— —

19.6 

H O O H —CH₂— —

19.7 

H O O H —CH₂— —

19.8 

H O O H —CH₂— —

19.9 

H O O H —CH₂— —

19.10

H O O H —CH₂— —

19.11

H O O H —CH₂— —

19.12 19.13 H O O H —CH₂— —

19.14 H O O H —CH₂— —

19.15 H O O H —CF₂— —

19.16 H O O H

—

19.17 H O O H

—

7.0 7.1 H O O H —CH₃ —CH₃

7.2 H N O H

—CH₃

13.0  13.1  H N O H —CH₂—

13.2  H N O H —CH₂—

Substance X¹ R¹ X² R² R³ R⁴ R⁵ X³ X⁴ R⁶ R⁷ R⁸

20,0  20.1  O —CH₃ O

H —CH₃ O O

H 20.2  O —CH₃ O

H —CH₃ O O

H 20.3  O —CH₃ O

H —CH₃ O O

H 20.4  O —CH₃ O

H —CH₃ O O

H

8.0 8.1 O —CH₃ O

H —CH₃ O O —CH₃

H 8.2 O —CH₃ O

H —CH₃ O O

H 8.3 O —CH₃ O

—CH₃ O O

H Substance X¹ X² R³ R² R¹ R⁴ X⁴ X³ R⁸ R⁶ R⁵ R⁷

14.0  14.1  O —CH₃ O —CH₃

—CH₃ O O

H 14.2  O —CH₃ O

—CH₃ O O

H Substance R¹ X² X¹ R⁴ R³ R² R⁵ X⁴ X³ R⁸ R⁷ R⁶

18.0  18.1 

O H

—CH₃

O H

—CH₃ 18.2 

O H

—CH₃

O H

—CH₃ 18.3 

O H

—CH₃

O H

—CH₃ 18.4 

O H

—CH₃

O H

—CH₃

6.0 6.1

O H

—CH₃ —CH₃ O O H

—CH₃ 6.2

O H

—CH₃ O O H

12.0  12.1  —CH₃ O O H

—CH₃

O H

H 12.2  —CH₃ O O H

O H

—CH₃

21.0  21.1  —CH₃ O O

—CH₃ O O

9.0 9.1 —CH₃ O O

—CH₃ O O H

9.2 —CH₃ O O

O H

15.0  15.1 

O H

—CH₃ O O

Substance X² R² R³ R⁴ X³ R⁵ R⁶ X⁴ R⁷ R⁸ X¹ R¹

22.0  22.1  O —CH₃

—CH₃ —CH₃ O

—CH₃

10.0  10.1  O —CH₃

—CH₃ —CH₃ O

H O —CH₃ 10.2  O

—CH₃ —CH₃ O H O —CH₃

16.0  16.1  O

H O —CH₃ —CH₃ O

—CH₃

TABLE 2 2,5-diamino-3,6-dihydroterephthalic acid derivatives SubstanceX¹ X² R³ R¹

2.0

2.1 O O

—CH₃

2.2 O O

—CH₃

2.3 O O

—CH₃

2.4 O O

—CH₃

2.5 O O

—C₂H₅

2.6 O O

—CH₃

2.7 O O

—CH₃

2.8 O O

—CH₃

2.9 O O

—CH₃

2.10 O O

—CH₃

2.11 O O

—CH₃

2.12 O O

—CH₃

2.13 O O

—CH₃

2.14 O O

—CH₃

2.15 O O

—CH₃

2.16 O O

—CH₃

2.17 O O

—CH₃

2.18 O O

—CH₃

2.19 O O

—CH₃

2.20 O O

—CH₃

2.21 O O

—CH₃

2.22 O O

—CH₃

2.24 O O

—CH₃

2.25 O O —C₄H₉ —CH₃

2.26 O O

—CH₃

2.27 O O

—CH₃

2.28 O O

—CH₃

2.29 O O

—CH₃

2.30 O O

—CH₃

2.31 O O

—CH₃

2.32 O O

—CH₃

2.33 O O

—CH₃

2.34 O O

—CH₃

2.35 O O

—CH₃

2.36 O O

—CH₃

2.37 O O

—CH₃

2.38 O O

—CH₃

2.39 O O

—CH₃

2.40 O O

—CH₃

2.41 O O

—CH₃

2.42 O O

—CH₃

2.43 O O

—CH₃ 2.44 O O

—CH₃ 2.45 O O

—CH₃ 2.46 O O

—CH₃ 2.47 O O

—CH₃ 2.48 O O

—CH₃ 2.49 O O

—CH₃ 2.50 O O

—CH₃ 2.51 O O

—CH₃ 2.52 O O

—CH₃ 2.53 O O

—CH₃ 2.54 O O

—CH₃ 2.55 O O

—CH₃ 2.56 O O

—CH₃ 2.57 O O

—CH₃ 2.58 O O

—CH₃ 2.59 O O

—CH₃ 2.60 O O

—CH₃ 2.61 O O

—CH₃ 2.62 O O

—CH₃ 2.63 O O

—CH₃ 2.64 O O

—CH₃ 2.65 O O

—CH₃ 2.66 O O

—CH₃ 2.67 O O

—CH₃ 2.68 O O

—CH₃ 2.69 O O

—CH₃ 2.70 O O

—CH₃ 2.71 O O

—CH₃ 2.72 O O

—CH₃ 2.73

—CH₃ 2.74 O N

2.75 O N

2.76 O O

—CH₃ 2.77 O O

—CH₃ 2.79 O O

—CH₃ Substance R² R^(4′) R^(4′) X⁴ X³

2.0

2.1 H H H O O

2.2 —CH₃ H H O O

2.3 H H H O O

2.4 H H H O O

2.5 H H H O O

2.6 H H H O O

2.7 H H H O O

2.8 H H H O O

2.9 H H H O O

2.10 H H H O O

2.11 H H H O O

2.12 H H H O O

2.13 H H H O O

2.14 H H H O O

2.15 H H H O O

2.16 H H H O O

2.17 H H H O O

2.18 H H H O O

2.19 —CH₃ H H O O

2.20 H H H O O

2.21 H H H O O

2.22 H H H O O

2.24 H H H O O

2.25 H H H O O

2.26 H H H O O

2.27 H H H O O

2.28 H H H O O

2.29 —CH₃ H H O O

2.30 H H H O O

2.31 —CH₃ H H O O

2.32 —CH₃ H H O O

2.33 —CH₃ H H O O

2.34

H H O O

2.35 H H H O O

2.36 —CH₃ H H O O

2.37 H H H O O

2.38

H H O O

2.39

H H O O

2.40

H H O O

2.41

H H O O

2.42

H H O O

2.43 H H H O O 2.44 —CH₃ F F O O 2.45 —CH₃ F F O O 2.46

F F O O 2.47

F F O O 2.48 —CH₃ H H O O 2.49 —CH₃ H H O O 2.50 —CH₃ H H O O 2.51 —CH₃H H O O 2.52 —CH₃ H H O O 2.53 —CH₃ H H O O 2.54 —CF₃ H H O O 2.55 —CF₃H H O O 2.56 —CF₃ H H O O 2.57 —CF₃ H H O O 2.58 —CF₃ H H O O 2.59 —CF₃H H O O 2.60

H H O O 2.61

H H O O 2.62

H H O O 2.63

H H O O 2.64

H H O O 2.65

H H O O 2.66

H H O O 2.67

H H O O 2.68

H H O O 2.69 —CH₃ H H O O 2.70

H H O O 2.71

H H O O 2.72

H H O O 2.73

H H O O 2.74 H H H N O 2.75

H H N O 2.76 —CH₃

O O 2.78

O O 2.79

O O Substance R⁸ R^(8′) R⁵ R⁶

2.0

2.1 H H —CH₃ H

2.2 H H —CH₃ —CH₃

2.3 H H —CH₃ H

2.4 H H —CH₃ H

2.5 H H —CH₃ H

2.6 H H —CH₃ H

2.7 H H —CH₃ H

2.8 H H —CH₃ H

2.9 H H —CH₃ H

2.10 H H —CH₃ H

2.11 H H —CH₃ H

2.12 H H —CH₃ H

2.13 H H —CH₃ H

2.14 H H —CH₃ H

2.15 H H —CH₃ H

2.16 H H —CH₃ H

2.17 H H —CH₃ H

2.18 H H —CH₃ H

2.19 H H —CH₃ —CH₃

2.20 H H —CH₃ H

2.21 H H —CH₃ H

2.22 H H —CH₃ H

2.24 H H —CH₃ H

2.25 H H —CH₃ H

2.26 H H —CH₃ H

2.27 H H —CH₃ H

2.28 H H —CH₃ H

2.29 H H —CH₃ —CH₃

2.30 H H —CH₃ H

2.31 H H —CH₃ —CH₃

2.32 H H —CH₃ —CH₃

2.33 H H —CH₃ —CH₃

2.34 H H —CH₃

2.35 H H —CH₃ H

2.36 H H —CH₃ —CH₃

2.37 H H —CH₃ H

2.38 H H —CH₃

2.39 H H —CH₃

2.40 H H —CH₃

2.41 H H —CH₃

2.42 H H —CH₃

2.43 H H —CH₃ H 2.44 F F —CH₃ —CH₃ 2.45 F F —CH₃ —CH₃ 2.46 F F —CH₃

2.47 F F —CH₃

2.48 H H —CH₃ —CH₃ 2.49 H H —CH₃ —CH₃ 2.50 H H —CH₃ —CH₃ 2.51 H H —CH₃—CH₃ 2.52 H H —CH₃ —CH₃ 2.53 H H —CH₃ —CH₃ 2.54 H H —CH₃ —CF₃ 2.55 H H—CH₃ —CF₃ 2.56 H H —CH₃ —CF₃ 2.57 H H —CH₃ —CF₃ 2.58 H H —CH₃ —CF₃ 2.59H H —CH₃ —CF₃ 2.60 H H —CH₃

2.61 H H —CH₃

2.62 H H —CH₃

2.63 H H —CH₃

2.64 H H —CH₃

2.65 H H —CH₃

2.66 H H —CH₃

2.67 H H —CH₃

2.68 H H —CH₃

2.69 H H —CH₃ —CH₃ 2.70 H H —CH₃

2.71 H H —CH₃

2.72 H H —CH₃

2.73 H H —CH₃

2.74 H H

H 2.75 H H

2.76

—CH₃ —CH₃ 2.78

—CH₃

2.79

—CH₃

Substance R⁷

2.0

2.1

2.2

2.3

2.4

2.5

2.6

2.7

2.9

2.9

2.10

2.11

2.12

2.13

2.14

2.15

2.16

2.17

2.18

2.19

2.20

2.21

2.22

2.24

2.25 —C₄H₉

2.26

2.27

2.28

2.29

2.30

2.31

2.32

2.33

2.34

2.35

2.36

2.37

2.38

2.39

2.40

2.41

2.42

2.43

2.44

2.45

2.46

2.47

2.48

2.49

2.50

2.51

2.52

2.53

2.54

2.55

2.56

2.57

2.58

2.59

2.60

2.61

2.62

2.63

2.64

2.65

2.66

2.67

2.68

2.69

2.70

2.71

2.72

2.73

2.74

2.75

2.76

2.78

2.79

Substanz X¹ X² R³ R¹ R² R⁴ X⁴ X³ R⁸ R⁵ R⁶ R⁷

37.0 37.1

—CH₃ —CH₃ H

H —CH₃ —CH₃

37.2

—CH₃ H

H

—CH₃

R^(4′) R^(8′)

37.0 37.1 H H 37.2 H H Substance X¹ X² R³ R¹ R² R⁴ X⁴ X³ R⁸ R⁵ R⁶ R⁷37.3

— —CH₃ H

H — —CH₃

37.4

— —CH₃ H

H — —CH₃

23.0 23.1

—CH₃ H O O H —CH₃ —CH₃

30.0 30.1 O O

—CH₃ —CH₃ H

—CH₃ —CH₃

Substance R^(4′) R^(8′) 37.3 H H 37.4 H H

23.0 23.1 H H

30.0 30.1 H

Substanz X¹ X² R³ R² R¹ R⁴ X⁴

39.0

39.1 O O

—CH₂— — H O

39.2 O O

—CH₂— — H O

39.3 O O

—CH₂— — H O

39.4 O O

—CH₂— — H O

39.5 O O

—CH₂— — H O

39.6 O O

—CH₂— — H O

39.7 O O

—CH₂— — H O

39.8 O O

—CH₂— — H O

39.9 O O

—CH₂— — H O

39.10 O O

—CH₂— — H O

39.11 O O

—CH₂— — H O

39.12 O O

—CH₂— — H O 39.13 O O

—CH₂— — H O 39.14 O O

—CH₂— — H O 39.15 O O

—CF₂— — H O 39.16 O O

— H O 39.17 O O

— H O 39.18 O O

—CH₂— — H O 39.19 O O

—CH₂— — H O 39.20 O O

—CF₂— — H O 39.21 O O

— H O 39.22 O O

— H O Substanz X³ R⁸ R⁶ R⁵ R⁷ R^(4′) R^(8′)

39.0

39.1 O H —CH₂— —

H H

39.2 O H —CH₂— —

H H

39.3 O H —CH₂— —

H H

39.4 O H —CH₂— —

H H

39.5 O H —CH₂— —

H H

39.6 O H —CH₂— —

H H

39.7 O H —CH₂— —

H H

39.8 O H —CH₂— —

H H

39.9 O H —CH₂— —

H H

39.10 O H —CH₂— —

H H

39.11 O H —CH₂— —

H H

39.12 O H —CH₂— —

H H 39.13 O H —CH₂— —

H H 39.14 O H —CH₂— —

H H 39.15 O H —CF₂— —

H H 39.16 O H

—

H H 39.17 O H

—

H H 39.18 O H —CH₂— —

H H 39.19 O H —CH₂— —

H H 39.20 O H —CF₂— —

H H 39.21 O H

—

H H 39.22 O H

—

H H SUBSTANCE X¹ X² R³ R² R¹ R⁴ X⁴ X³ R⁸ R⁶ R⁵ R⁷ R^(4′)

25.0 25.1 O O

—CH₂— H O O H —CH₃ —CH₃

H 25.2 O O

—CH₂— H N O H

—CH₃

H

32.0 32.1 O O

—CH₃ H N O H —CH₂—

H 32.2 O O

—CH₃ H N O H —CH₂—

H SUBSTANCE R^(8′)

25.0 25.1 H 25.2 H

32.0 32.1 H 32.2 H Substance X¹ R¹ X² RE² R³ R⁴ R⁵ X³ X⁴ R⁶ R⁷ R⁸

40.0 40.1 O —CH₃ O

H —CH₃ O O

H 40.2 O —CH₃ O

H —CH₃ O O

H 40.3 O —CH₃ O

H —CH₃ O O

H 40.4 O —CH₃ O

H —CH₃ O O

H

26.0 26.1 O —CH₃ O

H —CH₃ O O —CH₃

H 26.2 O —CH₃ O

H —CH₃ O O

H 26.3 O —CH₃ O

—CH₃ O O

H Substance R^(4′) R^(8′)

40.0 40.1 H H 40.2 H H 40.3 H H 40.4 H H

26.0 26.1 H H 26.2 H H 26.3

H Substance X¹ R¹ X² R⁴ R² R³ R⁵ X³ X⁴ R⁶ R⁷ R⁸ R^(4′)

33.0 33.1 O —CH₃ O —CH₃

—CH₃ O O

H +113 CH₃ 33.2 O —CH₃ O

—CH₃ O O

H

Substance R^(8′)

33.0 33.1 H 33.2 H Substance R¹ X² X¹ R⁴ R³ R² R⁵ X³ X³ R⁸ R⁷ R⁶ R^(4′)R^(8′)

38.0 38.1

O H

—CH₃

O H

—CH₃ H H 38.2

O H

—CH₃

O H

—CH₃ H H 38.3

O H

—CH₃

O H

—CH₃ H H 38.4

O H

—CH₃

O H

—CH₃ H H

24.0 24.1

O H

—CH₃ —CH₃ O O H

—CH₃ H H 24.2

O H

—CH₃ O O H

H H

31.0 31.1 —CH₃ O O H

—CH₃

O H

H H H 31.2 —CH₃ O O H

O H

—CH₃ H H Substance R¹ X² X¹ R^(4′) R³ R² R⁵ X⁴ X³ R^(8′) R⁷ R⁶

41.0 41.1 —CH₃ O O

—CH₃ O O

27.0 27.1 —CH₃ O O

—CH₃ O O H

p 27.2 —CH₃ O O

O H

Substance R⁴ R⁸

41.0 41.1 H H

27.0 27.1 H H 27.2 H H Substance R¹ X² X¹ R⁴ R³ R² R⁵ X⁴ X³ R⁵ R⁷ R^(8′)R^(4′) R⁸

34.0 34.1

O H

—CH₃ —CH₃ O O

H H Substance X² R² R³ R⁴ X³ R⁵ R⁶ X⁴ R⁷ R⁸ X¹

43.0 43.1 O —CH₃

—CH₃ —CH₃ O

29.0 29.1 O —CH₃

—CH₃ —CH₃ O

H O 29.2 O

—CH₃ —CH₃ O H O

36.0 36.1 O

H O —CH₃ —CH₃ O

Substance R¹ R^(4′) R^(8′)

43.0 43.1 —CH₃ —CH₃ —CH₃

29.0 29.1 —CH₃ —CH₃ —CH₃ 29.2 —CH₃ H H

36.0 36.1 —CH₃ H H

TABLE 3 Substituted 2,5-diaminoterephthalic acid dinitriles Substrate R³R²

3.0

3.1

H

3.2

—CH₃

3.3

H

3.4

H

3.5

H

3.6

H

3.7

H

3.8

H

3.9

H

3.10

H

3.11

H

3.12

H

3.13

H

3.14

H

3.15

H

3.16

H

3.17

—CH₃

3.18

H

3.19

H

3.20

H

3.21

H

3.22 —C₄H₉ H

3.23

H

3.24

H

3.25

H

3.26

—CH₃

3.27

H

3.28

—CH₃

3.29

—CH₃

3.30

—CH₃

3.31

3.32

H

3.33

—CH₃

3.34

H

3.35

3.36

3.37

3.38

3.39

3.40

H 3.41

—CH₃ 3.42

—CH₃ 3.43

—CH₃ 3.44

—CH₃ 3.45

—CH₃ 3.46

—CH₃ 3.47

—CF₃ 3.48

—CF₃ 3.49

—CF₃ 3.50

—CF₃ 3.51

—CF₃ 3.52

—CF₃ 3.53

3.54

3.55

3.56

3.57

3.58

3.59

3.60

3.61

3.62

—CH₃ 3.63

3.64

3.65

3.66

3.67

H 3.68

3.69

—CH₃ 3.70

3.71

R⁴ R⁸ R⁶

3.0

3.1 H H H

3.2 H H —CH₃

3.3 H H H

3.4 H H H

3.5 H H H

3.6 H H H

3.7 H H H

3.8 H H H

3.9 H H H

3.10 H H H

3.11 H H H

3.12 H H H

3.13 H H H

3.14 H H H

3.15 H H H

3.16 H H H

3.17 H H —CH₃

3.18 H H H

3.19 H H H

3.20 H H H

3.21 H H H

3.22 H H H

3.23 H H H

3.24 H H H

3.25 H H H

3.26 H H —CH₃

3.27 H H H

3.28 H H —CH₃

3.29 H H —CH₃

3.30 H H —CH₃

3.31 H H

3.32 H H H

3.33 H H —CH₃

3.34 H H H

3.35 H H

3.36 H H

3.37 H H

3.38 H H

3.39 H H

3.40 H H H 3.41 H H —CH₃ 3.42 H H —CH₃ 3.43 H H —CH₃ 3.44 H H —CH₃ 3.45H H —CH₃ 3.46 H H —CH₃ 3.47 H H —CF₃ 3.48 H H —CF₃ 3.49 H H —CF₃ 3.50 HH —CF₃ 3.51 H H —CF₃ 3.52 H H —CF₃ 3.53 H H

3.54 H H

3.55 H H

3.56 H H

3.57 H H

3.58 H H

3.59 H H

3.60 H H

3.61 H H

3.62 H H —CH₃ 3.63 H H

3.64 H H

3.65 H H

3.66 H H

3.67 H H H 3.68 H H

3.69

—CH₃ 3.70

3.71

R⁷

3.0

3.1

3.2

3.3

3.4

3.5

3.6

3.7

3.8

3.9

3.10

3.11

3.12

3.13

3.14

3.15

3.16

3.17

3.18

3.19

3.20

3.21

3.22 —C₄H₉

3.23

3.24

3.25

3.26

3.27

3.28

3.29

3.30

3.31

3.32

3.33

3.34

3.35

3.36

3.37

3.38

3.39

3.40

3.41

3.42

3.43

3.44

3.45

3.46

3.47

3.48

3.49

3.50

3.51

3.52

3.53

3.54

3.55

3.56

3.57

3.58

3.59

3.60

3.61

3.62

3.63

3.64

3.65

3.66

3.67

3.68

3.69

3.70

3.71

Substance R² R³ R⁴³ R⁶ R⁷ R⁸

48.0 48.1

H

H 48.2

H

H 48.3

H

H 48.4

H

H

44.0 44.1

H —CH₃

H 44.2

H

H 44.3

H Substance R⁸ R² R³ R⁶ R⁷ R⁴

46.0 46.1 H —CH₃

H 46.2 H

H Substance R⁴ R³ R² R⁸ R⁷ R⁶

49.0 49.1

45.0 45.1

H

47.0 47.1 H

TABLE 4 Substituted 2,5-diamino-3,6-dihydroterephthalic acid dinitrilesSubstance R³ R² R⁴ R^(4′) R⁸ R^(8′) R⁶

4.0 —CH₃ —CH₃ —CH₃ —CH₃

4.1

H —CH₃ —CH₃ —CH₃ —CH₃ H

4.2

—CH₃ —CH₃ —CH₃ —CH₃ —CH₃ —CH₃

4.3

H —CH₃ —CH₃ —CH₃ —CH₃ H Substance R⁷

4.0

4.1

4.2

4.3

Substance R³ R²

4.4

H

4.5

H

4.6

H

4.7

H

4.8

H

4.9

H

4.10

H

4.11

H

4.12

H

4.13

H

4.14

H

4.15

H

4.16

H

4.17

—CH₃

4.18

H

4.19

H

4.20

H

4.21

H

4.22 —C₄H₉ H

4.23

H

4.24

H

4.25

H

4.26

—CH₃

4.27

H

4.28

—CH₃

4.29

—CH₃

4.30

—CH₃

4.31

H

4.32

—CH₃

4.33

H

4.34

4.35

4.36

4.37

4.38

4.38

H 4.40

—CH₃ 4.41

—CH₃ 4.42

—CH₃ 4.43

—CH₃ 4.44

—CH₃ 4.45

—CH₃ 4.46

—CF₃ 4.47

—CF₃ 4.48

—CF₃ 4.49

—CF₃ 4.50

—CF₃ 4.51

—CF₃ 4.52

4.53

4.54

4.55

4.56

4.57

4.58

4.59

4.60

4.61

—CH₃ 4.62

4.63

4.64

4.65

4.66

H 4.67

4.68

—CH₃ 4.69

4.70

—R⁴ R⁸ R⁶

4.4 —CH₃ —CH₃ H

4.5 —CH₃ —CH₃ H

4.6 —CH₃ —CH₃ H

4.7 —CH₃ —CH₃ H

4.8 —CH₃ —CH₃ H

4.9 —CH₃ —CH₃ H

4.10 —CH₃ —CH₃ H

4.11 —CH₃ —CH₃ H

4.12 —CH₃ —CH₃ H

4.13 —CH₃ —CH₃ H

4.14 —CH₃ —CH₃ H

4.15 —CH₃ —CH₃ H

4.16 —CH₃ —CH₃ H

4.17 —CH₃ —CH₃ —CH₃

4.18 —CH₃ —CH₃ H

4.19 —CH₃ —CH₃ H

4.20 —CH₃ —CH₃ H

4.21 —CH₃ —CH₃ H

4.22 —CH₃ —CH₃ H

4.23 —CH₃ —CH₃ H

4.24 —CH₃ —CH₃ H

4.25 —CH₃ —CH₃ H

4.26 —CH₃ —CH₃ —CH₃

4.27 —CH₃ —CH₃ H

4.28 —CH₃ —CH₃ —CH₃

4.29 —CH₃ —CH₃ —CH₃

4.30 —CH₃ —CH₃ —CH₃

4.31 —CH₃ —CH₃

—CH₃ —CH₃ H

4.32 —CH₃ —CH₃ —CH₃

4.33 —CH₃ —CH₃ H

4.34 —CH₃ —CH₃

4.35 —CH₃ —CH₃

4.36 —CH₃ —CH₃

4.37 —CH₃ —CH₃

4.38 —CH₃ —CH₃

4.39 —CH₃ —CH₃ H 4.40 —CH₃ —CH₃ —CH₃ 4.41 —CH₃ —CH₃ —CH₃ 4.42 —CH₃ —CH₃—CH₃ 4.43 —CH₃ —CH₃ —CH₃ 4.44 —CH₃ —CH₃ —CH₃ 4.45 —CH₃ —CH₃ —CH₃ 4.46—CH₃ —CH₃ —CF₃ 4.47 —CH₃ —CH₃ —CF₃ 4.48 —CH₃ —CH₃ —CF₃ 4.49 —CH₃ —CH₃—CF₃ 4.50 —CH₃ —CH₃ —CF₃ 4.51 —CH₃ —CH₃ —CF₃ 4.52 —CH₃ —CH₃

4.53 —CH₃ —CH₃

4.54 —CH₃ —CH₃

4.55 —CH₃ —CH₃

4.56 —CH₃ —CH₃

4.57 —CH₃ —CH₃

4.58 —CH₃ —CH₃

4.59 —CH₃ —CH₃

4.60 —CH₃ —CH₃

4.61 —CH₃ H —CH₃ 4.62 —CH₃ H

4.63 —CH₃ H

4.64 —CH₃ H

4.65 —CH₃ H

4.66 —CH₃ H H 4.67 —CH₃ H

4.68

—CH₃ 4.69

4.70

Substance R⁷ R^(4′) R^(8′)

4.4

—CH₃ —CH₃

4.5

—CH₃ —CH₃

4.6

—CH₃ —CH₃

4.7

—CH₃ —CH₃

4.8

—CH₃ —CH₃

4.9

—CH₃ —CH₃

4.10

—CH₃ —CH₃

4.11

—CH₃ —CH₃

4.12

—CH₃ —CH₃

4.13

—CH₃ —CH₃

4.14

—CH₃ —CH₃

4.15

—CH₃ —CH₃

4.16

—CH₃ —CH₃

4.17

—CH₃ —CH₃

4.18

—CH₃ —CH₃

4.19

—CH₃ —CH₃

4.20

—CH₃ —CH₃

4.21

—CH₃ —CH₃

4.22 —C₄H₉ —CH₃ —CH₃

4.23

—CH₃ —CH₃

4.24

—CH₃ —CH₃

4.25

—CH₃ —CH₃

4.26

—CH₃ —CH₃

4.27

—CH₃ —CH₃

4.28

—CH₃ —CH₃

4.29

—CH₃ —CH₃

4.30

—CH₃ —CH₃

4.31

—CH₃ —CH₃

—CH₃ —CH₃

4.32

—CH₃ —CH₃

4.33

—CH₃ —CH₃

4.34

—CH₃ —CH₃

4.35

—CH₃ —CH₃

4.36

—CH₃ —CH₃

4.37

—CH₃ —CH₃

4.38

—CH₃ —CH₃

4.39

—CH₃ —CH₃ 4.40

—CH₃ 1'CH₃ 4.41

—CH₃ —CH₃ 4.42

—CH₃ —CH₃ 4.43

—CH₃ —CH₃ 4.44

—CH₃ —CH₃ 4.45

—CH₃ —CH₃ 4.46

—CH₃ —CH₃ 4.47

—CH₃ —CH₃ 4.48

—CH₃ —CH₃ 4.49

—CH₃ —CH₃ 4.50

—CH₃ —CH₃ 4.51

—CH₃ —CH₃ 4.52

—CH₃ —CH₃ 4.53

—CH₃ —CH₃ 4.54

—CH₃ —CH₃ 4.55

—CH₃ —CH₃ 4.56

—CH₃ —CH₃ 4.57

—CH₃ —CH₃ 4.58

—CH₃ —CH₃ 4.59

—CH₃ —CH₃ 4.60

—CH₃ —CH₃ 4.61

—CH₃ —CH₃ 4.62

—CH₃ —CH₃ 4.63

—CH₃ —CH₃ 4.64

—CH₃ —CH₃ 4.65

—CH₃ —CH₃ 4.66

—CH₃ —CH₃ 4.67

—CH₃ —CH₃ 4.68

—CH₃ —CH₃ 4.69

—CH₃ —CH₃ 4.70

—CH₃ —CH₃ Substance R² R³ R⁴ R⁶ R⁷ R⁸ R^(8′) R^(4′)

56.0 56.1

—CH₃

—CH₃ —CH₃ —CH₃ 56.2

—CH₃

—CH₃ —CH₃ —CH₃ 56.3

—CH₃

—CH₃ —CH₃ —CH₃ 56.4

—CH₃

—CH₃ —CH₃ —CH₃ Substance R² R³ R⁶ R⁷ R⁸ R^(8′) R⁴ R^(4′)

50.0 50.1

—CH₃

—CH₃ —CH₃ —CH₃ —CH₃ 50.2

—CH₃ —CH₃ —CH₃ —CH₃ 50.3

—CH₃

—CH₃ SUBSTANCE R⁸ R^(8′) R³ R⁶ R⁷ R⁴ R^(4′) R²

53.0 53.1 —CH₃ —CH₃

—CH₃ —CH₃ —CH₃ 53.2 —CH₃ —CH₃

—CH₃ —CH₃

Substance R^(4′) R³ R² R^(8′) R⁷ R⁶ R⁴ R⁸

57.0 57.1

—CH₃ —CH₃

51.0 51.1

H

—CH₃ —CH₃ Substance R⁴ R^(4′) R³ R² R⁶ R⁷ R^(8′) R⁸

54.0 54.1 —CH₃ —CH₃

—CH₃

52.0

52.1

—CH₃ —CH₃

55.0

55.1 —CH₃ —CH₃

58.0

58.1

1. An organic electroluminescent device comprising at least one emitterlayer which includes at least one 2,5-diaminoterephthalic acidderivative having formula 1a:

wherein the ring A is a triply unsaturated benzene ring wherein R^(4′)and R^(8′) are omitted, or the ring A is an unsaturated ring having twoisolated double bonds in the 1,2-position and the 4,5-position, and R¹⁰is —CN or —C(═X¹)—X²R¹; R¹¹ is —CN or —C(═X³)—X⁴R⁵; X¹ and X³, which arethe same or different, are oxygen, sulphur or imino; X² and X⁴, whichare the same or different, are oxygen, sulphur or substituted orunsubstituted amino; R¹ to R⁸, R^(4′) and R^(8′) are the same ordifferent and are hydrogen, C1-C20 alkyl, aryl, heteroaryl, wherein aryland heteroaryl can be substituted singly or multiply with the same ordifferent radicals di-C1-C3-amino, C1-C10 alkoxy, C1-C4 alkyl, cyano,fluorine, chlorine and bromine as well as phenyl; R⁴ and R⁸ can also behalogen, nitro, cyano or amino, R² to R⁴, R⁶ to R⁸, R^(4′) and R^(8′)can also be trifluoromethyl, 2-fluorophenyl, 3-fluorophenyl,4-fluorophenyl, 2,4-difluorophenyl, 2,6-difluorophenyl,2,3,4,5-tetrafluorophenyl or pentafluorophenyl; and wherein thefollowing radicals can form a saturated or unsaturated ring X¹ and X²,R¹ and R², R² and X², R² and R³, R³ and R⁴, R⁴ and X³, X³ and X⁴, R⁵ andX⁴, R⁶ and X⁴, R⁶ and R⁷, R⁷ and R⁸, R⁸ and X¹, R³ and R^(4′), R⁷ andR^(8′), R⁴ and R^(4′), and R⁸ and R^(8′), to which ring further ringscan be fused.
 2. The device of claim 1, wherein X¹ and X³ are oxygen. 3.The device of claim 1, wherein R¹⁰ and R¹¹ are —CN.
 4. The device ofclaim 1, wherein the 2,5-diaminoterephthalic acid derivative has aformula 1:

wherein X¹ and X³ are the same or different atoms or groups, oxygen,sulphur or amino; X² and X⁴ are the same or different atoms or groups,oxygen, sulphur or amino, wherein the amino nitrogen can be substituted;R¹, R², R⁵ and R⁶ are the same or different and are hydrogen, C1-C20alkyl; aryl, substituted aryl, heteroaryl, or substituted heteroaryl; R⁴and R⁸ are the same or different and are hydrogen, C1-C20 alkyl,halogen, nitro, cyano, amino, aryl, substituted aryl, heteroaryl, orsubstituted heteroaryl; and R³ and R⁷ are the same or different and arearyl, substituted aryl, heteroaryl, or substituted heteroaryl.
 5. Thedevice of claim 4, wherein R³ and R⁷ are the same or different and arearyl or substituted aryl.
 6. The device of claim 5, wherein R³ and R⁷are the same or different and are phenyl, substituted phenyl, naphthylor substituted naphthyl.
 7. The device of claim 6, wherein R³ and R⁷ arethe same or different and are phenyl substituted singly or multiply withthe same or different radicals selected from di-C1-C3-amino, C1-C10alkoxy, C1-C4 alkyl, cyano, fluorine, chlorine, bromine and phenyl. 8.The device of claim 1, wherein the 2,5-diaminoterephthalic acidderivative has a formula 20a:

wherein R² and R³ are members of a 5- or 6-membered ring, forming asaturated or unsaturated heterocycle; and R⁶ and R⁷ are members of a 5-or 6-membered ring, forming a saturated or unsaturated heterocycle. 9.The device of claim 8, wherein R² and R³ are members of a 5- or6-membered ring, forming a saturated heterocycle; and R⁶ and R⁷ aremembers of a 5- or 6-membered ring, forming a saturated heterocycle. 10.A 2,5-diaminoterephthalic acid derivative having a formula 20a:

wherein R² and R³ are members of a 5- or 6-membered ring, forming asaturated or unsaturated heterocycle; R⁶ and R⁷ are members of a 5- or6-membered ring, forming a saturated or unsaturated heterocycle; R⁴ andR⁸ are the same or different and are hydrogen, C1-C20 alkyl, halogen,nitro, cyano, amino, aryl, substituted aryl, heteroaryl, or substitutedheteroaryl R¹⁰ is —CN or —C(═X¹)—X²R¹; R¹¹ is —CN or —C(═X³)—X⁴R⁵; andR¹ and R⁵ are the same or different substituents and are hydrogen,C1-C20 alkyl; aryl, substituted aryl, heteroaryl, or substitutedheteroaryl;
 11. The 2,5-diaminoterephthalic acid derivative of claim 10,wherein X¹, X², X³ and X⁴ are oxygen and R¹ and R⁵ are the same ordifferent and are C1-C4 alkyl.
 12. The 2,5-diaminoterephthalic acidderivative of claim 10, wherein R¹⁰ and R¹¹ are —CN.
 13. The2,5-diaminoterephthalic acid derivative of claim 10, wherein R⁴ and R⁸are hydrogen.